The present invention relates to 4-quinolinol derivatives and agricultural and horticultural fungicides containing them as active ingredients.
JP-01246263A, JP-05202032A, JP-05271222A and JP-07285938A, which were published prior to the filing date of the present application, disclose that quinoline derivatives having a substituent, such as aryloxy, arylthio, amino, pyrimidyloxy, pyrimidylthio or benzoyl group, at 4-position of quinoline skeleton are effective against plant pathogenic fungi and useful as agricultural and horticultural fungicides. However, it has never known that a quinoline derivative having an acyloxy group at 4-position of quinoline skeleton has an excellent fungicidal activity.
And, JP-03128355A discloses 4-acyloxyquinoline derivatives structurally similar to the compound of the present invention and insecticidal and acaricidal agents containing them as active ingredients. However, it has never known that these compounds are effective against plant pathogenic fungi.
Many active agents having control effect against various plant diseases were discovered and various agricultural and horticultural fungicides containing them as active ingredients have been developed. Due to some problems, such as an appearance of resistant fungi, however, fungicides having higher control effect are needed.
Thus, an object of the present invention is to provide a new agricultural and horticultural fungicide having higher control effect.
The present inventors concentrated on solving the above-mentioned problem. As the result, it was found that among 4-quinolinol derivatives, 4-quinolinol derivatives having specific substituents at all of the 2, 3 and 5 to 8 positions of quinoline skeleton and their acid addition salts show excellent fungicidal activity against various plant pathogenic fungi causing blast of rice, brown spot of rice, powdery mildew of Cucurbitaceae, anthracnose of potato and the like, and thereby the present invention was completed.
Accordingly, the present invention relates to a 4-quinolinol derivative represented by the general formula (I): 
wherein
R1 represents
a hydrogen atom,
an alkali metal,
an alkaline earth metal, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1-C18 alkyl group,
an optionally substituted C2-C18 alkenyl group,
an optionally substituted C3-C10 cycloalkyl group,
an optionally substituted phenyl lower alkyl group,
an optionally substituted phenoxy lower alkyl group,
an optionally substituted aryl group,
OR5 in which R5 is an optionally substituted lower alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl lower alkyl group or an optionally substituted phenoxy lower alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1-C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 represents an optionally substituted lower alkyl group;
R3 represents
an optionally substituted C1-C18 alkyl group,
an optionally substituted lower alkenyl group, or
an optionally substituted lower alkoxy group; or
R2 and R3 together represent xe2x80x94(CH2)mxe2x80x94 in which m is 3 or 4; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1-C10 alkyl group,
an optionally substituted lower alkenyl group,
an optionally substituted lower alkynyl group,
an optionally substituted C1-C10 alkoxy group,
an optionally substituted C3-C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1-C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
a nitro group or
a cyano group,
and acid addition salts thereof as well as an agricultural and horticultural fungicide containing at least one of them.
In the 4-quinolinol derivatives represented by the aforementioned general formula (I),
R1 represents
a hydrogen atom,
an alkali metal, such as preferably sodium and potassium,
an alkaline earth metal, such as magnesium, calcium and barium, in which magnesium and calcium are preferable, or
COR4 in which R4 is
a hydrogen atom,
an optionally substituted C1-C18 alkyl group, preferably an optionally substituted C1-C8 alkyl group, more preferably a C1-C4 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,
an optionally substituted C2-C18 alkenyl group, preferably an optionally substituted C2-C8 alkenyl group, more preferably a C2-C4 alkenyl group, such as vinyl group CH2xe2x95x90CHxe2x80x94, allyl group CH2xe2x95x90CHCH2xe2x80x94 and 2-butenyl group CH3CHxe2x95x90CHCH2xe2x80x94,
an optionally substituted C3-C10 cycloalkyl group, preferably an optionally substituted C3-C6 cycloalkyl group,
an optionally substituted phenyl lower alkyl group,
an optionally substituted phenoxy lower alkyl group,
an optionally substituted aryl group,
OR5 in which R5 is an optionally substituted lower alkyl group, an optionally substituted aryl group, an optionally substituted heterocycle, an optionally substituted phenyl lower alkyl group or an optionally substituted phenoxy lower alkyl group, or
NR6R7 in which R6 and R7 are each a hydrogen atom, an optionally substituted C1-C6 alkyl group or an optionally substituted phenyl group, or R6 and R7 together with N may form a four- to six-membered ring containing one or two heteroatoms;
R2 represents an optionally substituted C1-C4 alkyl group;
R3 represents
an optionally substituted C1-C18 alkyl group, preferably an optionally substituted C1-C6 alkyl group, more preferably a C1-C4 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl,
an optionally substituted lower alkenyl group, or
an optionally substituted lower alkoxy group; or
R2 and R3 together represent xe2x80x94(CH2)mxe2x80x94 in which m is 3 or 4; and
W represents 1 to 4 substituents on the nucleus which may be identical or different and each of which is
a halogen atom,
an optionally substituted C1-C10 alkyl group,
an optionally substituted lower alkenyl group,
an optionally substituted lower alkynyl group,
an optionally substituted C1-C10 alkoxy group,
an optionally substituted C3-C10 cycloalkyl group,
an optionally substituted aryl group,
an optionally substituted aryloxy group,
NR8R9 in which R8 and R9 are each a hydrogen atom, an optionally substituted C1-C6 alkyl group or an optionally substituted phenyl group, or R8 and R9 together with N may form a four- to six-membered ring containing one or two heteroatoms,
COR10 in which R10 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
COOR11 in which R11 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted lower alkenyl group,
a nitro group, or
a cyano group.
Agriculturally and horticulturally acceptable acid addition salts of the 4-quinolinol derivative represented by the aforementioned general formula (I) mean salts generally usable in agriculture and horticulture, such as hydrochloride, nitrate, sulfate, phosphate and acetate.
The 4-quinolinol derivative represented by the aforementioned general formula (I) may be in the form of hydrate or solvate. Such hydrate and solvate of the compound represented by the general formula (I) are also included in the present invention.
Substituents which optionally present on the 4-quinoline derivative represented by the aforementioned general formula (I) include a halogen atom, such as fluorine, bromine and chlorine, a C1-C4 alkyl group, a C1-C4 alkoxy group, a hydroxyl group, a nitro group, a formyl group, a cyano group and the like.
The term xe2x80x9clower alkyl groupxe2x80x9d as used herein means an alkyl group containing about 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl.
The term xe2x80x9clower alkenyl groupxe2x80x9d as used herein means an alkenyl group containing about 2 to 4 carbon atoms, such as vinyl, (1- or 2-)propenyl or (1-, 2- or 3-)butenyl.
The term xe2x80x9clower alkynyl groupxe2x80x9d as used herein means an alkynyl group containing about 2 to 4 carbon atoms, such as ethynyl, (1- or 2-)propynyl or (1-, 2- or 3-)butynyl.
The term xe2x80x9clower alkoxy groupxe2x80x9d as used herein means an alkoxy group containing about 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxy or butyloxy.
The term xe2x80x9cC1-C18 alkyl groupxe2x80x9d as used herein means an alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
The term xe2x80x9cC2-C18 alkenyl groupxe2x80x9d as used herein means, for example, vinyl, (1- or 2-)propenyl, (1-, 2- or 3-)butenyl, (1-, 2-, 3- or 4-)pentenyl, (1-, 2-, 3-, 4- or 5-)hexenyl, (1-, 2-, 3-, 4-, 5- or 6-)heptenyl, (1-, 2-, 3-, 4-, 5-, 6- or 7-)octenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-)nonenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-)decenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-)undecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- or 11-)dodecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-)tridecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13-)tetradecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 14-)pentadecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- or 15-)hexadecenyl, (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- or 16-)heptadecenyl, or (1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- or 17-)octadecenyl.
The term xe2x80x9cC3-C10 cycloalkyl groupxe2x80x9d as used herein means, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.
The term xe2x80x9cC1-C10 alkoxy groupxe2x80x9d as used herein means, for example, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy or decyloxy.
The term xe2x80x9cphenyl lower alkyl groupxe2x80x9d as used herein means a phenylalkyl group having a C1-C4 alkyl moiety, such as benzyl, (1- or 2-)phenylethyl, (1-, 2- or 3-)phenylpropyl or (1-, 2-, 3- or 4-)phenylbutyl.
The term xe2x80x9cphenoxy lower alkyl groupxe2x80x9d as used herein means a phenoxyalkyl group having a C1-C4 alkyl moiety, such as phenoxymethyl, (1- or 2-)phenoxyethyl, (1-, 2- or 3-)phenoxypropyl or (1-, 2-, 3- or 4-)phenoxybutyl.
The following Table 1 specifically illustrates the compounds within the scope of the 4-hydroxyquinoline derivatives represented by the general formula (I) of the present invention.
Abbreviations used in Table 1 and Examples have following meanings.
Compounds of the general formula (I)xe2x80x2 which comprise a part of 4-quinolinol derivatives represented by the general formula (I) can be prepared by the known method as described in JP-03128355A according to the following scheme. 
Thus, a compound of the general formula (I)xe2x80x2 was synthesized by reacting a compound represented by the general formula (II) with a reagent represented by the general formula (III) or (IV) in the presence or absence of a base and by, if necessary, replacing a substituent of the thus obtained compound with a desired substituent. In the above formulae, R1 to R4 and W are as defined above. Example of the usable base includes organic amines, such as triethylamine and pyridine, or inorganic alkalis, such as sodium carbonate, potassium carbonate and sodium hydride. A compound of the general formula (II) as one of the starting materials was synthesized by a known method as described in J. Am. Chem. Soc., 70, 2402 (1948); Tetrahedron Lett., 27, 5323 (1986) using as a starting material, a substituted aniline which was commercially available or prepared by a known method. And, the reagent represented by the general formula (III) or (IV) is desirably used in an amount of 1 to 50 equivalents, preferably 1 to 10 equivalents with respect to the compound of the general formula (II). The reaction can be carried out in an inert organic solvent, such as dimethylformamide or dimethyl sulfoxide, at the temperature ranging from 0 to 140xc2x0 C.
Compounds represented by the aforementioned general formula (I) have an excellent fungicidal effect against blast of rice, brown spot of rice, powdery mildew of Cucurbitaceae, anthracnose of potato and the like.
When the present compound represented by the general formula (I) is used as an active ingredient of an agricultural and horticultural fungicide, it can be used as such. However, the present compound is generally used in any formulation, such as emulsifiable concentrate, solution, wettable powder, dust formulation, granule, oil solution, aerosol or flowable, which is prepared by combining the present compound with suitable adjuvants, such as solid carrier, liquid carrier, gaseous carrier, surfactant, dispersant and other additives.
Example of the solid carrier includes talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate and the like. Example of the liquid carrier includes alcohols, such as methanol, n-hexanol and ethylene glycol; ketones, such as acetone, methyl ethyl ketone and cyclohexanone; aliphatic hydrocarbons, such as n-hexane, kerosine and kerosene; aromatic hydrocarbons, such as toluene, xylene and methylnaphthalene; ethers, such as diethyl ether, dioxane and tetrahydrofuran; esters, such as ethyl acetate; nitrites, such as acetonitrile and isobutyronitrile; acid amides, such as dimethylformamide and dimethylacetamide; vegetable oils, such as soybean oil and cottonseed oil; dimethyl sulfoxide; water; and the like. And, example of the gaseous carrier includes LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.
Example of the surfactant or dispersant used for emulsification, dispersion and wetting includes alkyl sulfate esters, alkyl(aryl) sulfonate salts, polyoxyalkylene alkyl(aryl) ethers, polyhydric alcohol esters, lignin sulfonate salts and the like.
And, example of the adjuvant used for improving properties of a formulation includes carboxymethylcellulose, gum arabic, polyethylene glycol, calcium stearate and the like.
The above carrier, surfactant, dispersant and adjuvant may be used alone or in combination, if necessary.
Suitable amount of the active ingredient is generally 1 to 75% by weight in emulsifiable concentrate, generally 0.3 to 25% by weight in dust formulation, generally 1 to 90% by weight in wettable powder, or generally 0.5 to 10% by weight in granule.
Each of these formulations may be used as such or after dilution. Further, each of these formulations may be used in admixture with any other fungicide, insecticide, acaricide, herbicide, plant growth regulator, fertilizer and the like.
The application methods of the agricultural and horticultural fungicide of the present invention includes foliar application, paddy water application, soil treatment, nursery box application, seed disinfection and the like. Other application methods which are generally employed by those skilled in the art, however, can also show the desired effect of the present invention.